GB1199012A - A process for the manufacture of Polyene Compounds - Google Patents

A process for the manufacture of Polyene Compounds

Info

Publication number
GB1199012A
GB1199012A GB7094/67A GB709467A GB1199012A GB 1199012 A GB1199012 A GB 1199012A GB 7094/67 A GB7094/67 A GB 7094/67A GB 709467 A GB709467 A GB 709467A GB 1199012 A GB1199012 A GB 1199012A
Authority
GB
United Kingdom
Prior art keywords
group
formula
alkylenedioxy
dialkoxy
trimethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB7094/67A
Inventor
Basil Charles Leicester Weedon
Hans Johann Mayer
Ulrich Schwieter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
F Hoffmann La Roche AG
Original Assignee
F Hoffmann La Roche AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by F Hoffmann La Roche AG filed Critical F Hoffmann La Roche AG
Priority to GB7094/67A priority Critical patent/GB1199012A/en
Priority to CH140568A priority patent/CH496686A/en
Priority to IL29393A priority patent/IL29393A/en
Priority to DE19681668240 priority patent/DE1668240A1/en
Priority to US703247A priority patent/US3576880A/en
Priority to NL6801967A priority patent/NL6801967A/xx
Priority to BE710620D priority patent/BE710620A/xx
Priority to IE172/68A priority patent/IE32553B1/en
Priority to SE01867/68A priority patent/SE356977B/xx
Priority to FR1575581D priority patent/FR1575581A/fr
Publication of GB1199012A publication Critical patent/GB1199012A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/20—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by carboxyl groups or halides, anhydrides, or (thio)esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/10—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by etherified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

1,199,012. Polyene compounds. F. HOFFMANN-LA ROCHE & CO. A.G., and B. C. L. WEEDON. 14 Feb., 1968 [14 Feb., 1967], No. 7094/67. Heading C2C. The invention comprises aldehydes of the general formula in which R<SP>1</SP> is oxo, C 1 -C 7 alkylenedioxy or dialkoxy and R<SP>3</SP> represents CHO. They may be prepared by reducing an acetylenic compound of formula in which R<SP>2</SP> is a protecting group and R<SP>4</SP> is C 1 -C 7 alkylenedioxy or dialkoxy, with an alkali metal (e.g. Li) aluminium hydride to yield an olefinic compound of formula removing the protecting groups R<SP>2</SP> and R<SP>4</SP> by acid hydrolysis, reintroducing the R<SP>4</SP> group, if desired, and oxidizing the alcohol product, e.g. with manganese dioxide or chromic acid, to the desired aldehyde. Suitable protecting groups R<SP>2</SP> are those of formula in which R<SP>5</SP> is a C 1 -C 7 group and R<SP>6</SP> and R<SP>7</SP> each represent a C 1 -C 7 alkyl group or together form a trimethylene group. The acetylenic compound referred to above may be obtained by protecting the hydroxy group of cis-3- methyl - pent - 2 - en - 4 - yn - 1 - ol (e.g. by treating with isopropenyl methyl ether) and reacting the resisting alcohol of formula with a 2,6,6 - trimethyl - 4 - (C 1 -C 7 alkylenedioxy) - 2 - cyclohexen - 1 - one or a 2,6,6- trimethyl - 4,4 - dialkoxy - 2 - cyclohexen - 1 -one by means of a metal-organic reaction, e.g. by a Grignard reaction. Those aldehydes, in which R<SP>1</SP> is an alkylenedioxy or dialkoxy group may also be prepared by reacting a 2,6,6-trimethyl- 4 - (alkylenedioxy) - cyclohex - 2 - en - 1 - one or a 2,6,6 - trimethyl - 4,4 - dialkoxy - cyclohex- 2-en-1-one with cis-3-methyl-pent-2-en-4-yrrl-ol by a Grignard reaction, oxidizing the hydroxymethyl group of the resulting acetylenic alcohol and reducing the triple bond to a double bond. Those aldehydes in which R<SP>1</SP> is an oxo group may be prepared by this method with the additional step of hydrolysing with an acid the product at any stage. The aldehydes described above may be oxidized to give compounds of Formula (I) in which R is a C 1 -C 7 alkyl group. The oxidation may be carried out by means of silver oxide at 0-50‹ C. and the product may be converted to an ester by means of a diazoalkane, a C 1 -C 7 alkanol or an alkyl halide.
GB7094/67A 1967-02-14 1967-02-14 A process for the manufacture of Polyene Compounds Expired GB1199012A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
GB7094/67A GB1199012A (en) 1967-02-14 1967-02-14 A process for the manufacture of Polyene Compounds
CH140568A CH496686A (en) 1967-02-14 1968-01-30 Process for the preparation of polyene compounds
IL29393A IL29393A (en) 1967-02-14 1968-01-30 Process for the manufacture of alpha-hydroxycyclohexenyl pentadienoic acids and pentadienol and pentadienal intermediates therefor
DE19681668240 DE1668240A1 (en) 1967-02-14 1968-02-01 Process for the preparation of polyene compounds
US703247A US3576880A (en) 1967-02-14 1968-02-06 5(2,6,6-trimethyl - 1 - hydroxy-cyclohex-2-enyl) -3 methyl-penta-2,4-dien-1-al derivatives
NL6801967A NL6801967A (en) 1967-02-14 1968-02-12
BE710620D BE710620A (en) 1967-02-14 1968-02-12
IE172/68A IE32553B1 (en) 1967-02-14 1968-02-12 A process for the manufacture of polyene compounds
SE01867/68A SE356977B (en) 1967-02-14 1968-02-13
FR1575581D FR1575581A (en) 1967-02-14 1968-02-14

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7094/67A GB1199012A (en) 1967-02-14 1967-02-14 A process for the manufacture of Polyene Compounds

Publications (1)

Publication Number Publication Date
GB1199012A true GB1199012A (en) 1970-07-15

Family

ID=9826509

Family Applications (1)

Application Number Title Priority Date Filing Date
GB7094/67A Expired GB1199012A (en) 1967-02-14 1967-02-14 A process for the manufacture of Polyene Compounds

Country Status (10)

Country Link
US (1) US3576880A (en)
BE (1) BE710620A (en)
CH (1) CH496686A (en)
DE (1) DE1668240A1 (en)
FR (1) FR1575581A (en)
GB (1) GB1199012A (en)
IE (1) IE32553B1 (en)
IL (1) IL29393A (en)
NL (1) NL6801967A (en)
SE (1) SE356977B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925419A (en) * 1970-06-22 1975-12-09 Merck & Co Inc 5-Cyclic ethylene acetals of 5-oxocyclopentane heptanoic acids and esters
US4006188A (en) * 1975-06-25 1977-02-01 Zoecon Corporation Cycloalkenones
US4111992A (en) * 1976-09-15 1978-09-05 Hoffmann-La Roche Inc. Preparation of food coloring agents
DE3264786D1 (en) * 1981-11-04 1985-08-22 Basf Ag Acetylene derivatives, process for their preparation and their use in the regulation of the growth of plants
EP0112441A3 (en) * 1982-11-18 1984-10-17 Firmenich Sa Acetylenic carbinols, their use as starting compounds in the synthesis of beta-damascenon and allenic carbinols as intermediates in said synthesis, and process for their preparation

Also Published As

Publication number Publication date
CH496686A (en) 1970-09-30
FR1575581A (en) 1969-07-25
DE1668240A1 (en) 1971-07-22
SE356977B (en) 1973-06-12
IE32553B1 (en) 1973-09-19
BE710620A (en) 1968-08-12
IL29393A (en) 1971-03-24
IE32553L (en) 1968-08-14
NL6801967A (en) 1968-08-15
US3576880A (en) 1971-04-27

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Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]